Compositions comprising hydrophilic silica particulates

ABSTRACT

The present invention relates to structured surfactant compositions comprising a detergent surfactant and hydrophilic silica particulates to be used in granular detergent compositions. The preferred silica particulate is hydrophilic precipitated silica. The process for making a structured surfactant composition comprising a detergent surfactant and hydrophilic silica particulates is also included. The present invention encompasses a structured surfactant composition consisting essentially of: (a) from about 35% to about 60% of a detergent surfactant; (b) from about 1% to about 20% of hydrophylic, finely-divided silica particulate; and (c) from about 15% to about 25% moisture.

FIELD OF THE INVENTION

The present invention relates to structured surfactant compositionscomprising a detergent surfactant and hydrophilic silica particulates tobe used in granular detegent compositions. The preferred silicaparticulate is hydrophilic precipitated silica. The process for making astructured surfactant composition comprising a detergent surfactant andhydrophilic silica particulates is also included.

BACKGROUND OF THE INVENTION

It is desired to increase the active level of detergent surfactants incompositions comprising said surfactants in order to facilitate themanufacture of detergent compositions containing high active levels. Inaddition, it is also desirable to have surfactant compositions that arepumpable and generally easy to transport and transfer from onemanufacturing location to a granulation site. One way to meet theseneeds is by mixing a chemical structuring agent to the detergentsurfactant. Prior art includes EPO 508 543 published Oct. 14, 1992 andU.S. Pat. No. 4,925,585 granted May 15, 1990.

It has now been found that incorporating hydrophilic, finely-dividedsilica particulates as a highly-preferred structuring agent withdetergent surfactant enables the formation of structured surfactantcompositions which have high levels of active. Preferably, the detergentsurfactant is in an aqueous paste form. Structuring of the paste meansthe addition of a chemical in a solid, liquid, or solution form tochange the structure of the paste or modify its physical characteristicsto facilitate the manufacture of high active detergent agglomerateswhich otherwise are not easily obtainable under normal operatingconditions. In addition, when such structured surfactant compositionsare mixed with other detergent adjuvants such as additional surfactants,detergent builders, inorganic salts, silica, and mixtures thereof toform granular detergent compositions, such granules are free flowing andeasy to transport and transfer.

SUMMARY OF THE INVENTION

The invention encompasses a structured surfactant composition consistingessentially of:

(a) from about 35% to about 60% of a detergent surfactant;

(b) from about 1% to about 20% of hydrophilic, finely-divided silicaparticulate; and

(c) from about 15% to about 25% moisture.

The invention further encompasses a granular detergent compositioncomprising:

(a) from about 2% to about 70% of a structured surfactant composition,the surfactant composition consisting essentially of:

(i) from about 35% to about 60% of a detergent surfactant;

(ii) from about 1% to about 20% of hydrophilic, finely-divided silicaparticulate; and

(iii) from about 15% to about 25% moisture; and

(b) from about 30% to about 98% other detergent adjuvants selected fromthe group consisting of other detergent surfactants, detergent builders,silica, and mixtures thereof.

A process for making structured surfactant compositions is alsoincluded.

All documents referenced herein are incorporated by reference.

DETAILED DESCRIPTION OF THE INVENTION

This invention relates to compositions with a detergent surfactant andhydrophilic, finely-divided silica particulate.

Ingredients, as well as optional ingredients, as well as the process formaking a granular detergent composition or an additive composition for adetergent composition are described in detail hereinafter.

Structured Surfactant Composition

The structured surfactant composition of the present invention comprisesby weight:

(a) from about 35% to about 60%, preferably from about 35% to about 50%,most preferably from about 40% to about 45% of a detergent surfactant;

(b) from about 1% to about 20%, preferably from about 1% to about 10%,most preferably from about 2% to about 5%, of hydrophilic,finely-divided silica particulate; and

(c) from about 15% to about 25% moisture, wherein the ratio of thesilica particulate to moisture is from about 1:5 to about 1:25, morepreferably from about 1:5 to about 1:7.5.

The structured surfactant composition can be mixed with other detergentingredients to form detergent compositions. If the structured surfactantis directly made into a detergent composition, the detergent compositionwould comprise from about 20% to about 65%, preferably from about 30% toabout 65%, most preferably from about 45% to about 65% structuredsurfactant composition. The granular detergent composition preferablyhas a particle size of a maximum of 5% on 14 Tyler mesh.

The particulate silica is added to the surfactant paste, which typicallycontains 15% to about 25% moisture, as well as salts which are theby-product of neutralization. The particulate silica absorbs the waterand a hardened continuous paste is formed. When shear force is appliedto the hardened paste, the paste becomes a flowable liquid, which iseasily dispersed into fine droplets by using any conventional high-shearagglomerating mixer. The droplets are added with other powderingredients to form individual particles with have a particle size of amaximum of 5% on 14 Tyler mesh and a minimum of 5% through 100 Tylermesh. The droplets form particles inside a typical agglomerating mixer.These droplets once formed into a particle, do not re-form a continuoushardened paste. This results in the formation of particle agglomeratesto the specific particle size distribution that is required to maintainsolubility, handling, etc.

Detergent Surfactant

The detergent surfactant is any surfactant selected from the group ofconsisting of anionics, zwitterionics, ampholytics, cationics, andmixtures thereof. Preferably, the detergent surfactant is anionicsurfactant. Most preferably, the detergent surfactant is ethoxylatedanionic surfactant.

The anionic surfactant can be selected from:

(a) linear or branched chain alkyl benzene sulfonate having an C8-20alkyl chain, preferably C10-18 alkyl chain, and most preferably a C12-16alkyl chain;

(b) alkyl sulfate having a C8-20 alkyl chain, preferably C14-18 alkylchain, most preferably C12-16 alkyl chain;

(c) mixtures thereof.

Preferred is Alkylalkoxy sulfate comprising an alkyl portion of from 6to 18 carbon atoms and an alkoxy portion comprising, an average, fromabout 0.5 to about 20 moles of alkoxy, preferably ethoxy, units, morepreferably from about 0.5 to about 5 ethoxy units.

An anionic surfactant that is most preferable is the alkyl ether sulfateof the formula R--E_(n) SO₃ M, wherein:

(i) R is C8-20; and preferably, C12-15, alkyl chain (mixed chain);

(ii) E is an ethoxy unit;

(iii) n is from 1-20; preferably, n=3; and

(iv) M is a suitable cation, preferably sodium ion.

Useful anionic surfactants include water-soluble salts of2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbonatoms in the acyl group and from about 9 to about 23 carbon atoms in thealkane moiety; water-soluble salts of olefin sulfonates containing fromabout 12 to 24 carbon atoms; and beta-alkyloxy alkane sulfonatescontaining from about 1 to 3 carbon atoms in the alkyl group and fromabout 8 to 20 carbon atoms in the alkane moiety.

Water-soluble salts of the higher fatty acids, i.e., "soaps", also areuseful anionic surfactants herein. Soaps can be made by directsaponification of fats and oils or by the neutralization of free fattyacids. Examples of soaps are the sodium, potassium, ammonium, andalkylolamonium salts of higher fatty acids containing from about 8 toabout 24 carbon atoms, and preferably from about 12 to about 18 carbonatoms. Particularly useful are the sodium and potassium salts of themixtures of fatty acids derived from coconut oil and tallow, i.e.,sodium or potassium tallow and coconut soaps.

Other anionic surfactants useful herein include:

Sodium alkyl glyceryl ether sulfonates, especially those ethers ofhigher alcohols derived from tallow and coconut oil;

Sodium coconut oil fatty acid monoglyceride sulfonates and sulfates;

Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates,and sodium or potassium salts of methyl ester R--CH(SO₃ M)--COOR',wherein R is C₈ -C₂₂ alkyl or alkenyl, R' is C₁ -C₄ alkyl, and M is acounter ion, preferably Na or K, such as disclosed in WO-93-05013,published Mar. 18, 1992; sulfonates;

Alpha-sulfonated fatty acid alkyl ether surfactant of the formulaR'--C(SO3)H--C(O)--OR", wherein R' is C8-20; most preferably C8-18,alkyl chain; and R" is C1-C4 alkyl, preferably methyl;

Secondary alkyl sulfates having an alkyl chain of from 10 to 20 carbonatoms; and

Alkyl ethoxy carboxylates of the formula RO(CH₂ CH₂ O)_(x) CH₂ COO⁻ M⁺,wherein R is a C₆ to C₁₈ alkyl; x ranges from 0 to 10, and theethoxylate distribution is such that on a weight basis, the amount ofmaterial where x is 0 is less than 20%, the amount of material where xis greater than 7 is less than 25%, and wherein the average x is 2-4when the average R is C₁₃ or less, and is 3-6 when R is greater than C₁₃; and M is an alkali metal, alkali earth metal, ammonium, mono-, di-,and tri-ethanol ammonium.

One or various aqueous pastes of the salts of anionic surfactants ispreferred for use in the present invention. It is preferred that themoisture in the surfactant aqueous paste is as low as possible, whilemaintaining paste fluidity, and minimizing the amount of free water thatmay need to be removed, by drying for example, since low moisture leadsto a higher concentration of the surfactant in the finished particle.Preferably the paste contains from about 10% to about 40% water, morepreferably from about 15% to about 30% water, and most preferably fromabout 20% to about 30% water.

The activity of the surfactant paste is at least 30% and can go up toabout 90%; preferred activities are: 70-80%.

Cationic surfactants can also be used as a detergent surfactant hereinand suitable quaternary ammonium surfactants are selected from mono C₆-C₁₆, preferably C₆ -C₁₀ N-alkyl or alkenyl ammonium surfactants whereinremaining N positions are substituted by methyl, hydroxyethyl orhydroxypropyl groups.

Ampholytic surfactants can also be used as a detergent surfactantherein, which include aliphatic derivatives of heterocyclic secondaryand tertiary amines; zwitterionic surfactants which include derivativesof aliphatic quaternary ammonium, phosphonium and sulfonium compounds;water-soluble salts of esters of alpha-sulfonated fatty acids; alkylether sulfates; water-soluble salts of olefin sulfonates; beta-alkyloxyalkane sulfonates; betaines having the formula R(R¹)₂ N⁺ R² COO⁻,wherein R is a C₆ -C₁₈ hydrocarbyl group, preferably a C₁₀ -C₁₆ alkylgroup or C₁₀ -C₁₆ acylamido alkyl group, each R¹ is typically C₁ -C₃alkyl, preferably methyl and R₂ is a C₁ -C₅ hydrocarbyl group,preferably a C₁ -C₃ alkylene group, more preferably a C₁ -C₂ alkylenegroup. Examples of suitable betaines include coconutacylamidopropyldimethyl betaine; hexadecyl dimethyl betaine; C₁₂₋₁₄acylamidopropylbetaine; C₈₋₁₄ acylamidohexyldiethyl betaine; 4[C₁₄₋₁₆acylmethylamidodiethylammonio]-1-carboxybutane; C₁₆₋₁₈acylamidodimethylbetaine; C₁₂₋₁₆ acylamidopentanediethylbetaine; and[C₁₂₋₁₆ acylmethylamidodimethylbetaine. Preferred betaines are C₁₂₋₁₈dimethyl-ammonio hexanoate and the C₁₀₋₁₈ acylamidopropane (or ethane)dimethyl (or diethyl) betaines; and the sultaines having the formula(R(R¹)₂ N⁺ R² SO₃ ⁻ wherein R is a C₆ -C₁₈ hydrocarbyl group, preferablya C₁₀ -C₁₆ alkyl group, more preferably a C₁₂ -C₁₃ alkyl group, each R¹is typically C₁ -C₃ alkyl, preferably methyl, and R² is a C₁ -C₆hydrocarbyl group, preferably a C₁ -C₃ alkylene or, preferably,hydroxyalkylene group. Examples of suitable sultaines include C₁₂ -C₁₄dimethylammonio-2-hydroxypropyl sulfonate, C₁₂ -C₁₄ amido propylammonio-2-hydroxypropyl sultaine, C₁₂ -C₁₄ dihydroxyethylammonio propanesulfonate, and C₁₆₋₁₈ dimethylammonio hexane sulfonate, with C₁₂₋₁₄amido propyl ammonio-2-hydroxypropyl sultaine being preferred.

Hydrophilic Silica Particulates

The structured surfactant compositions of the present inventioncontains, in addition to a detergent surfactant, from about 0.2% toabout 20%, preferably from about 1% to about 10%, most preferably fromabout 2% to about 5%, of hydrophilic, finely-divided silica particulate.Preferably, the particulate is a hydrophilic precipitated silica. Suchmaterials are extremely fine-particle size silicon dioxides. Its surfacearea ranges preferably from 140 to 550 m² /g as measured by the BETnitrogen adsorption method. The surface of the silica has both internaland external surface area which allows for the easy absorption ofliquids. Dibutyl Phthlate absorption is the method used to determine theabsorptive capability of precepitated silica. Generally, a precipitatedsilica can adsorb 2 to 3 times its weight.

Precipitated silica materials usually appear in the form ofagglomerates. The average agglomerate size of the silica range fromabout 50 to 100 microns. The silica agglomerates may be milled byvarious known methods to reduce the agglomerate size to the range of 2to 15 microns. The pH of the silica is normally from about 5.5 to about7.0.

The hydrophilic silica can also be a fumed silica. Hydrophilicprecipitated silica materials useful herein are commercially availablefrom Degussa Corporation under the names SIPERNAT 22S, 22LS, 50S.

Detergent Adjuvants

Preferably, the detergent adjuvants are from about 35% to about 99% ofthe detergent composition. The compositions herein can optionallyinclude one or more other detergent adjunct materials or other materialsfor assisting or enhancing cleaning performance, treatment of thesubstrate to be cleaned, or to modify the aesthetics of the detergentcomposition (e.g., perfumes, colorants, dyes, etc.). The following areillustrative examples of such adjunct materials.

Other detergent surfactants include surfactants described above. Inaddition, a hydrotrope, or mixture of hydrotropes, can be present in thelaundry detergent bar. Preferred hydrotropes include the alkali metal,preferably sodium, salts of tolune sulfonate, xylene sulfonate, cumenesulfonate, sulfosuccinate, and mixtures thereof. Preferably, thehydrotrope, in either the acid form or the salt form, and beingsubstantially anhydrous, is added to the linear alkyl benzene sulfonicacid prior to its neutralization. The hydrotrope will preferably bepresent at from about 0.5% to about 5% of the laundry detergent bar.

Detergent builders can optionally be included in the compositions hereinto assist in controlling mineral hardness. Inorganic as well as organicbuilders can be used. Builders are typically used in fabric launderingcompositions to assist in the removal of particulate soils.

The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder. Liquidformulations typically comprise from about 5% to about 50%, moretypically about 5% to about 30%, by weight, of detergent builder.Granular formulations typically comprise from about 10% to about 80%,more typically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called "weak" builders(as compared with phosphates) such as citrate, or in the so-called"underbuilt" situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ :Na₂ O ratio in the range 1.6:1 to3.2:1 and layered silicates, such as the layered sodium silicatesdescribed in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P.Rieck. NaSKS-6 is the trademark for a crystalline layered silicatemarketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlikezeolite builders, the Na SKS-6 silicate builder does not containaluminum. NaSKS-6 has the delta-Na₂ SiO₅ morphology form of layeredsilicate. It can be prepared by methods such as those described inGerman DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferredlayered silicate for use herein, but other such layered silicates, suchas those having the general formula NaMSi_(x) O_(2x+1).yH₂ O wherein Mis sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and yis a number from 0 to 20, preferably 0 can be used herein. Various otherlayered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, asthe alpha, beta and gamma forms. As noted above, the delta-Na₂ SiO₅(NaSKS-6 form) is most preferred for use herein. Other silicates mayalso be useful such as for example magnesium silicate, which can serveas a crispening agent in granular formulations, as a stabilizing agentfor oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    M.sub.z (zAlO.sub.2).sub.y ].xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builders include the C₅ -C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, palmitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Hydrophilic silica particulates as described above is a preferreddetergent adjuvant.

Other Adjunct Ingredients

Chelating Agents

The detergent compositions herein may also optionally contain one ormore iron and/or manganese chelating agents. Such chelating agents canbe selected from the group consisting of amino carboxylates, aminophosphonates, polyfunctionally-substituted aromatic chelating agents andmixtures therein, all as hereinafter defined. Without intending to bebound by theory, it is believed that the benefit of these materials isdue in part to their exceptional ability to remove iron and manganeseions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents includeethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates,nitrilotriacetates, ethylenediamine tetraproprionates,triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, andethanoldiglycines, alkali metal, ammonium, and substituted ammoniumsalts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in thecompositions of the invention when at lease low levels of totalphosphorus are permitted in detergent compositions, and includeethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred,these amino phosphonates to not contain alkyl or alkenyl groups withmore than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also usefulin the compositions herein. See U.S. Pat. No. 3,812,044, issued May 21,1974, to Connor et al. Preferred compounds of this type in acid form aredihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediaminedisuccinate ("EDDS"), especially the [S,S] isomer as described in U.S.Pat. No. 4,704,233, Nov. 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from about0.1% to about 10% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

Clay Soil Removal/Anti-redeposition Agents

The compositions of the present invention can also optionally containwater-soluble ethoxylated amines having clay soil removal andantiredeposition properties. Granular detergent compositions whichcontain these compounds typically contain from about 0.01% to about10.0% by weight of the water-soluble ethoxylates amines; liquiddetergent compositions typically contain about 0.01% to about 5%.

The most preferred soil release and anti-redeposition agent isethoxylated tetraethylene-pentamine. Exemplary ethoxylated amines arefurther described in U.S. Pat. No. 4,597,898, VanderMeer, issued Jul. 1,1986. Another group of preferred clay soil removal-antiredepositionagents are the cationic compounds disclosed in European PatentApplication 111,965, Oh and Gosselink, published Jun. 27, 1984. Otherclay soil removal/antiredeposition agents which can be used include theethoxylated amine polymers disclosed in European Patent Application111,984, Gosselink, published Jun. 27, 1984; the zwitterionic polymersdisclosed in European Patent Application 112,592, Gosselink, publishedJul. 4, 1984; and the amine oxides disclosed in U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985. Other clay soil removal and/or antiredeposition agents known in the art can also be utilized in thecompositions herein. Another type of preferred antiredeposition agentincludes the carboxy methyl cellulose (CMC) materials. These materialsare well known in the art.

Polymeric Dispersing Agents

Polymeric dispersing agents can advantageously be utilized at levelsfrom about 0.1% to about 7%, by weight, in the compositions herein,especially in the presence of zeolite and/or layered silicate builders.Suitable polymeric dispersing agents include polymeric polycarboxylatesand polyethylene glycols, although others known in the art can also beused. It is believed, though it is not intended to be limited by theory,that polymeric dispersing agents enhance overall detergent builderperformance, when used in combination with other builders (includinglower molecular weight polycarboxylates) by crystal growth inhibition,particulate soil release peptization, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing orcopolymerizing suitable unsaturated monomers, preferably in their acidform. Unsaturated monomeric acids that can be polymerized to formsuitable polymeric polycarboxylates include acrylic acid, maleic acid(or maleic anhydride), fumaric acid, itaconic acid, aconitic acid,mesaconic acid, citraconic acid and methylenemalonic acid. The presencein the polymeric polycarboxylates herein or monomeric segments,containing no carboxylate radicals such as vinylmethyl ether, styrene,ethylene, etc. is suitable provided that such segments do not constitutemore than about 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived fromacrylic acid. Such acrylic acid-based polymers which are useful hereinare the water-soluble salts of polymerized acrylic acid. The averagemolecular weight of such polymers in the acid form preferably rangesfrom about 2,000 to 10,000, more preferably from about 4,000 to 7,000and most preferably from about 4,000 to 5,000. Water-soluble salts ofsuch acrylic acid polymers can include, for example, the alkali metal,ammonium and substituted ammonium salts. Soluble polymers of this typeare known materials. Use of polyacrylates of this type in detergentcompositions has been disclosed, for example, in Diehl, U.S. Pat. No.3,308,067, issued Mar. 7, 1967.

Acrylic/maleic-based copolymers may also be used as a preferredcomponent of the dispersing/anti-redeposition agent. Such materialsinclude the water-soluble salts of copolymers of acrylic acid and maleicacid. The average molecular weight of such copolymers in the acid formpreferably ranges from about 2,000 to 100,000, more preferably fromabout 5,000 to 75,000, most preferably from about 7,000 to 65,000. Theratio of acrylate to maleate segments in such copolymers will generallyrange from about 30:1 to about 1:1, more preferably from about 10:1 to2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers caninclude, for example, the alkali metal, ammonium and substitutedammonium salts. Soluble acrylate/maleate copolymers of this type areknown materials which are described in European Patent Application No.66915, published Dec. 15, 1982, as well as in EP 193,360, published Sep.3, 1986, which also describes such polymers comprisinghydroxypropylacrylate. Still other useful dispersing agents include themaleic/acrylic/vinyl alcohol terpolymers. Such materials are alsodisclosed in EP 193,360, including, for example, the 45/45/10 terpolymerof acrylic/maleic/vinyl alcohol.

Another polymeric material which can be included is polyethylene glycol(PEG). PEG can exhibit dispersing agent performance as well as act as aclay soil removal-antiredeposition agent. Typical molecular weightranges for these purposes range from about 500 to about 100,000,preferably from about 1,000 to about 50,000, more preferably from about1,500 to about 10,000.

Polyaspartate and polyglutamate dispersing agents may also be used,especially in conjunction with zeolite builders. Dispersing agents suchas polyaspartate preferably have a molecular weight (avg.) of about10,000.

Brightener

Any optical brighteners or other brightening or whitening agents knownin the art can be incorporated at levels typically from about 0.05% toabout 1.2%, by weight, into the detergent compositions herein.Commercial optical brighteners which may be useful in the presentinvention can be classified into subgroups, which include, but are notnecessarily limited to, derivatives of stilbene, pyrazoline, coumarin,carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles,5- and 6-membered-ring heterocycles, and other miscellaneous agents.Examples of such brighteners are disclosed in "The Production andApplication of Fluorescent Brightening Agents", M. Zahradnik, Publishedby John Wiley & Sons, New York (1982).

Specific examples of optical brighteners which are useful in the presentcompositions are those identified in U.S. Pat. No. 4,790,856, issued toWixon on Dec. 13, 1988. These brighteners include the PHORWHITE seriesof brighteners from Verona. Other brighteners disclosed in thisreference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; availablefrom Ciba-Geigy; Artic White CC and Artic White CWD, available fromHilton-Davis, located in Italy; the2-(4-stryl-phenyl)-2H-napthol[1,2-d]triazoles;4,4'-bis-(1,2,3-triazol-2-yl)-stil-benes; 4,4'-bis(stryl)bisphenyls; andthe aminocoumarins. Specific examples of these brighteners include4-methyl-7-diethyl-amino coumarin; 1,2-bis(-venzimidazol-2-yl)ethylene;1,3-diphenyl-phrazolines; 2,5-bis(benzoxazol-2-yl)thiophene;2-stryl-napth-[1,2-d]oxazole; and2-(stilbene-4-yl)-2H-naphtho-[1,2-d]triazole. See also U.S. Pat. No.3,646,015, issued Feb. 29, 1972 to Hamilton. Anionic brighteners arepreferred herein.

Suds Suppressors

Compounds for reducing or suppressing the formation of suds can beincorporated into the compositions of the present invention. Sudssuppression can be of particular importance in the so-called "highconcentration cleaning process" as described in U.S. Pat. Nos. 4,489,455and 4,489,574 and in front-loading European-style washing machines.

A wide variety of materials may be used as suds suppressors, and sudssuppressors are well known to those skilled in the art. See, forexample, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition,Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). One category ofsuds suppressor of particular interest encompasses monocarboxylic fattyacid and soluble salts therein. See U.S. Pat. No. 2,954,347, issued Sep.27, 1960 to Wayne St. John. The monocarboxylic fatty acids and saltsthereof used as suds suppressor typically have hydrocarbyl chains of 10to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitablesalts include the alkali metal salts such as sodium, potassium, andlithium salts, and ammonium and alkanolammonium salts.

The detergent compositions herein may also contain non-surfactant sudssuppressors. These include, for example: high molecular weighthydrocarbons such as paraffin, fatty acid esters (e.g., fatty acidtriglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈-C₄₀ ketones (e.g., stearone), etc. Other suds inhibitors includeN-alkylated amino triazines such as tri- to hexa-alkylmelamines or di-to tetra-alkyldiamine chlortriazines formed as products of cyanuricchloride with two or three moles of a primary or secondary aminecontaining 1 to 24 carbon atoms, propylene oxide, and monostearylphosphates such as monostearyl alcohol phosphate ester and monostearyldi-alkali metal (e.g., K, Na, and Li) phosphates and phosphate esters.The hydrocarbons such as paraffin and haloparaffin can be utilized inliquid form. The liquid hydrocarbons will be liquid at room temperatureand atmospheric pressure, and will have a pour point in the range ofabout -40° C. and about 50° C., and a minimum boiling point not lessthan about 110° C. (atmospheric pressure). It is also known to utilizewaxy hydrocarbons, preferably having a melting point below about 100° C.The hydrocarbons constitute a preferred category of suds suppressor fordetergent compositions. Hydrocarbon suds suppressors are described, forexample, in U.S. Pat. No. 4,265,779, issued May 5, 1981 to Gandolfo etal. The hydrocarbons, thus, include aliphatic, alicyclic, aromatic, andheterocyclic saturated or unsaturated hydrocarbons having from about 12to about 70 carbon atoms. The term "paraffin," as used in this sudssuppressor discussion, is intended to include mixtures of true paraffinsand cyclic hydrocarbons.

Another preferred category of non-surfactant suds suppressors comprisessilicone suds suppressors. This category includes the use ofpolyorganosiloxane oils, such as polydimethylsiloxane, dispersions oremulsions of polyorganosiloxane oils or resins, and combinations ofpolyorganosiloxane with silica particles wherein the polyorganosiloxaneis chemisorbed or fused onto the silica. Silicone suds suppressors arewell known in the art and are, for example, disclosed in U.S. Pat. No.4,265,779, issued May 5, 1981 to Gandolfo et al and European PatentApplication No. 89307851.9, published Feb. 7, 1990, by Starch, M. S.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839which relates to compositions and processes for defoaming aqueoussolutions by incorporating therein small amounts of polydimethylsiloxanefluids.

Mixtures of silicone and silanated silica are described, for instance,in German Patent Application DOS 2,124,526. Silicone defoamers and sudscontrolling agents in granular detergent compositions are disclosed inU.S. Pat. No. 3,933,672, Bartolotta et al, and in U.S. Pat. No.4,652,392, Baginski et al, issued Mar. 24, 1987.

An exemplary silicone based suds suppressor for use herein is a sudssuppressing amount of a suds controlling agent consisting essentiallyof:

(i) polydimethylsiloxane fluid having a viscosity of from about 20 cs.to about 1,500 cs. at 25° C.;

(ii) from about 5 to about 50 parts per 100 parts by weight of (i) ofsiloxane resin composed of (CH₃)₃ SiO_(1/2) units of SiO₂ units in aratio of from (CH₃)₃ SiO_(1/2) units and to SiO₂ units of from about0.6:1 to about 1.2:1; and

(iii) from about 1 to about 20 parts per 100 parts by weight of (i) of asolid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for acontinuous phase is made up of certain polyethylene glycols orpolyethylene-polypropylene glycol copolymers or mixtures thereof(preferred), or polypropylene glycol. The primary silicone sudssuppressor is branched/crosslinked and preferably not linear.

To illustrate this point further, typical liquid laundry detergentcompositions with controlled suds will optionally comprise from about0.001 to about 1, preferably from about 0.01 to about 0.7, mostpreferably from about 0.05 to about 0.5, weight % of said silicone sudssuppressor, which comprises (1) a nonaqueous emulsion of a primaryantifoam agent which is a mixture of (a) a polyorganosiloxane, (b) aresinous siloxane or a silicone resin-producing silicone compound, (c) afinely divided filler material, and (d) a catalyst to promote thereaction of mixture components (a), (b) and (c), to form silanolates;(2) at least one nonionic silicone surfactant; and (3) polyethyleneglycol or a copolymer of polyethylene-polypropylene glycol having asolubility in water at room temperature of more than about 2 weight %;and without polypropylene glycol. Similar amounts can be used ingranular compositions, gels, etc. See also U.S. Pat. No. 4,978,471,Starch, issued Dec. 18, 1990, and U.S. Pat. No. 4,983,316, Starch,issued Jan. 8, 1991, U.S. Pat. No. 5,288,431, Huber et al., issued Feb.22, 1994, and U.S. Pat. Nos. 4,639,489 and 4,749,740, Aizawa et al atcolumn 1, line 46 through column 4, line 35.

The silicone suds suppressor herein preferably comprises polyethyleneglycol and a copolymer of polyethylene glycol/polypropylene glycol, allhaving an average molecular weight of less than about 1,000, preferablybetween about 100 and 800. The polyethylene glycol andpolyethylene/polypropylene copolymers herein have a solubility in waterat room temperature of more than about 2 weight %, preferably more thanabout 5 weight %.

The preferred solvent herein is polyethylene glycol having an averagemolecular weight of less than about 1,000, more preferably between about100 and 800, most preferably between 200 and 400, and a copolymer ofpolyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300.Preferred is a weight ratio of between about 1:1 and 1:10, mostpreferably between 1:3 and 1:6, of polyethylene glycol:copolymer ofpolyethylene-polypropylene glycol.

The preferred silicone suds suppressors used herein do not containpolypropylene glycol, particularly of 4,000 molecular weight. They alsopreferably do not contain block copolymers of ethylene oxide andpropylene oxide, like PLURONIC L101.

Other suds suppressors useful herein comprise the secondary alcohols(e.g., 2-alkyl alkanols) and mixtures of such alcohols with siliconeoils, such as the silicones disclosed in U.S. Pat. Nos. 4,798,679,4,075,118 and EP 150,872. The secondary alcohols include the C₆ -C₁₆alkyl alcohols having a C₁ -C₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12.Mixtures of secondary alcohols are available under the trademarkISALCHEM 123 from Enichem. Mixed suds suppressors typically comprisemixtures of alcohol+silicone at a weight ratio of 1:5 to 5:1.

For any detergent compositions to be used in automatic laundry washingmachines, suds should not form to the extent that they overflow thewashing machine. Suds suppressors, when utilized, are preferably presentin a "suds suppressing amount. By "suds suppressing amount" is meantthat the formulator of the composition can select an amount of this sudscontrolling agent that will sufficiently control the suds to result in alow-sudsing laundry detergent for use in automatic laundry washingmachines.

The compositions herein will generally comprise from 0% to about 5% ofsuds suppressor. When utilized as suds suppressors, monocarboxylic fattyacids, and salts therein, will be present typically in amounts up toabout 5%, by weight, of the detergent composition. Preferably, fromabout 0.5% to about 3% of fatty monocarboxylate suds suppressor isutilized. Silicone suds suppressors are typically utilized in amounts upto about 2.0%, by weight, of the detergent composition, although higheramounts may be used. This upper limit is practical in nature, dueprimarily to concern with keeping costs minimized and effectiveness oflower amounts for effectively controlling sudsing. Preferably from about0.01% to about 1% of silicone suds suppressor is used, more preferablyfrom about 0.25% to about 0.5%. As used herein, these weight percentagevalues include any silica that may be utilized in combination withpolyorganosiloxane, as well as any adjunct materials that may beutilized. Monostearyl phosphate suds suppressors are generally utilizedin amounts ranging from about 0.1% to about 2%, by weight, of thecomposition. Hydrocarbon suds suppressors are typically utilized inamounts ranging from about 0.01% to about 5.0%, although higher levelscan be used. The alcohol suds suppressors are typically used at 0.2%-3%by weight of the finished compositions.

Fabric Softeners

Various through-the-wash fabric softeners, especially the impalpablesmectite clays of U.S. Pat. No. 4,062,647, Storm and Nirschl, issuedDec. 13, 1977, as well as other softener clays known in the art, canoptionally be used typically at levels of from about 0.5% to about 10%by weight in the present compositions to provide fabric softenerbenefits concurrently with fabric cleaning. Clay softeners can be usedin combination with amine and cationic softeners as disclosed, forexample, in U.S. Pat. No. 4,375,416, Crisp et al, Mar. 1, 1983 and U.S.Pat. No. 4,291,071, Harris et al, issued Sep. 22, 1981.

Additional Adjunct Ingredients

A wide variety of other ingredients useful in detergent compositions canbe included in the compositions herein, including other activeingredients, carriers, hydrotropes, processing aids, dyes or pigments,solvents for liquid formulations, solid fillers for bar compositions,etc. If high sudsing is desired, suds boosters such as the C₁₀ -C₁₆alkanolamides can be incorporated into the compositions, typically at1%-10% levels. The C₁₀ -C₁₄ monoethanol and diethanol amides illustratea typical class of such suds boosters. Use of such suds boosters withhigh sudsing adjunct surfactants such as the amine oxides, betaines andsultaines noted above is also advantageous. If desired, solublemagnesium salts such as MgCl₂, MgSO₄, and the like, can be added atlevels of, typically, 0.1%-2%, to provide additional suds and to enhancegrease removal performance.

Various detersive ingredients employed in the present compositionsoptionally can be further stabilized by absorbing said ingredients ontoa porous hydrophobic substrate, then coating said substrate with ahydrophobic coating. Preferably, the detersive ingredient is admixedwith a surfactant before being absorbed into the porous substrate. Inuse, the detersive ingredient is released from the substrate into theaqueous washing liquor, where it performs its intended detersivefunction.

To illustrate this technique in more detail, a porous hydrophobic silica(trademark SIPERNAT D10, DeGussa) is admixed with a proteolytic enzymesolution containing 3%-5% of C₁₃₋₁₅ ethoxylated alcohol (EO 7) nonionicsurfactant. Typically, the enzyme/surfactant solution is 2.5× the weightof silica. The resulting powder is dispersed with stirring in siliconeoil (various silicone oil viscosities in the range of 500-12,500 can beused). The resulting silicone oil dispersion is emulsified or otherwiseadded to the final detergent matrix. By this means, ingredients such asthe aforementioned enzymes, bleaches, bleach activators, bleachcatalysts, photoactivators, dyes, fluorescers, fabric conditioners andhydrolyzable surfactants can be "protected" for use in detergents,including liquid laundry detergent compositions.

Liquid detergent compositions can contain water and other solvents ascarriers. Low molecular weight primary or secondary alcohols exemplifiedby methanol, ethanol, propanol, and isopropanol are suitable. Monohydricalcohols are preferred for solubilizing surfactant, but polyols such asthose containing from 2 to about 6 carbon atoms and from 2 to about 6hydroxy groups (e.g., 1,3-propanediol, ethylene glycol, glycerine, and1,2-propanediol) can also be used. The compositions may contain from 5%to 90%, typically 10% to 50% of such carriers.

The detergent compositions herein will preferably be formulated suchthat, during use in aqueous cleaning operations, the wash water willhave a pH of between about 6.5 and about 11, preferably between about7.5 and 10.5. Liquid dishwashing product formulations preferably have apH between about 6.8 and about 9.0. Laundry products are typically at pH9-11. Techniques for controlling pH at recommended usage levels includethe use of buffers, alkalis, acids, etc., and are well known to thoseskilled in the art.

Dye Transfer Inhibiting Agents

The compositions of the present invention may also include one or morematerials effective for inhibiting the transfer of dyes from one fabricto another during the cleaning process. Generally, such dye transferinhibiting agents include polyvinyl pyrrolidone polymers, polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,manganese phthalocyanine, peroxidases, and mixtures thereof. If used,these agents typically comprise from about 0.01% to about 10% by weightof the composition, preferably from about 0.01% to about 5%, and morepreferably from about 0.05% to about 2%.

More specifically, the polyamine N-oxide polymers suitable for useherein contain units having the following structural formula: R--A_(x)--P; wherein P is a polymerizable unit to which an N--O group can beattached or the N--O group can form part of the polymerizable unit orthe N--O group can be attached to both units; A is one of the followingstructures: --NC(O)--, --C(O)O--, --S--, --O--, --N═; x is 0 or 1; and Ris aliphatic, ethoxylated aliphatics, aromatics, heterocyclic oralicyclic groups or any combination thereof to which the nitrogen of theN--O group can be attached or the N--O group is part of these groups.Preferred polyamine N-oxides are those wherein R is a heterocyclic groupsuch as pyridine, pyrrole, imidazole, pyrrolidine, piperidine andderivatives thereof.

The N--O group can be represented by the following general structures:##STR1## wherein R₁, R₂, R₃ are aliphatic, aromatic, heterocyclic oralicyclic groups or combinations thereof; x, y and z are 0 or 1; and thenitrogen of the N--O group can be attached or form part of any of theaforementioned groups. The amine oxide unit of the polyamine N-oxideshas a pKa<10, preferably pKa<7, more preferred pKa<6.

Any polymer backbone can be used as long as the amine oxide polymerformed is water-soluble and has dye transfer inhibiting properties.Examples of suitable polymeric backbones are polyvinyls, polyalkylenes,polyesters, polyethers, polyamide, polyimides, polyacrylates andmixtures thereof. These polymers include random or block copolymerswhere one monomer type is an amine N-oxide and the other monomer type isan N-oxide. The amine N-oxide polymers typically have a ratio of amineto the amine N-oxide of 10:1 to 1:1,000,000. However, the number ofamine oxide groups present in the polyamine oxide polymer can be variedby appropriate copolymerization or by an appropriate degree ofN-oxidation. The polyamine oxides can be obtained in almost any degreeof polymerization. Typically, the average molecular weight is within therange of 500 to 1,000,000; more preferred 1,000 to 500,000; mostpreferred 5,000 to 100,000. This preferred class of materials can bereferred to as "PVNO".

The most preferred polyamine N-oxide useful as dye transfer inhibitingpolymers in the detergent compositions herein ispoly(4-vinylpyridine-N-oxide) which as an average molecular weight ofabout 50,000 and an amine to amine N-oxide ratio of about 1:4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referredto as a class as "PVPVI") are also suitable for use herein. Preferablythe PVPVI has an average molecular weight range from 5,000 to 1,000,000,more preferably from 5,000 to 200,000, and most preferably from 10,000to 20,000. (The average molecular weight range is determined by lightscattering as described in Barth, et al., Chemical Analysis, Vol 113."Modern Methods of Polymer Characterization", the disclosures of whichare incorporated herein by reference.) The PVPVI copolymers typicallyhave a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1:1 to0.2:1, more preferably from 0.8:1 to 0.3:1, most preferably from 0.6:1to 0.4:1. These copolymers can be either linear or branched.

The present invention also may employ as a dye transfer inhibitor apolyvinylpyrrolidone ("PVP") having an average molecular weight of fromabout 5,000 to about 400,000, preferably from about 5,000 to about200,000, and more preferably from about 5,000 to about 50,000. PVP's areknown to persons skilled in the detergent field; see, for example,EP-A-262,897 and EP-A-256,696, incorporated herein by reference.Compositions containing PVP dye transfer inhibitors can also containpolyethylene glycol ("PEG") having an average molecular weight fromabout 500 to about 100,000, preferably from about 1,000 to about 10,000.Preferably, the ratio of PEG to PVP on a ppm basis delivered in washsolutions is from about 2:1 to about 50:1, and more preferably fromabout 3:1 to about 10:1.

Enzymes

Enzymes can be included in the formulations herein for a wide variety offabric laundering purposes, including removal of protein-based,carbohydrate-based, or triglyceride-based stains, for example, and forthe prevention of refugee dye transfer, and for fabric restoration. Theenzymes to be incorporated include proteases, amylases, lipases,cellulases, and peroxidases, as well as mixtures thereof. Other types ofenzymes may also be included. They may be of any suitable origin, suchas vegetable, animal, bacterial, fungal and yeast origin. However, theirchoice is governed by several factors such as pH-activity and/orstability optima, thermostability, stability versus active detergents,builders and so on. In this respect bacterial or fungal enzymes arepreferred, such as bacterial amylases and proteases, and fungalcellulases.

Enzymes are normally incorporated at levels sufficient to provide up toabout 5 mg by weight, more typically about 0.01 mg to about 3 mg, ofactive enzyme per gram of the composition. Stated otherwise, thecompositions herein will typically comprise from about 0.001% to about5%, preferably 0.01%-1% by weight of a commercial enzyme preparation.Protease enzymes are usually present in such commercial preparations atlevels sufficient to provide from 0.005 to 0.1 Anson units (AU) ofactivity per gram of composition.

Suitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8-12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE. The preparationof this enzyme and analogous enzymes is described in British PatentSpecification No. 1,243,784 of Novo. Proteolytic enzymes suitable forremoving protein-based stains that are commercially available includethose sold under the tradenames ALCALASE and SAVINASE by Novo IndustriesA/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (TheNetherlands). Other proteases include Protease A (see European PatentApplication 130,756, published Jan. 9, 1985) and Protease B (seeEuropean Patent Application Serial No. 87303761.8, filed Apr. 28, 1987,and European Patent Application 130,756, Bott et al, published Jan. 9,1985).

Amylases include, for example, -amylases described in British PatentSpecification No. 1,296,839 (Novo), RAPIDASE, InternationalBio-Synthetics, Inc. and TERMAMYL, Novo Industries.

The cellulase usable in the present invention include both bacterial orfungal cellulase. Preferably, they will have a pH optimum of between 5and 9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, issued Mar. 6, 1984, which discloses fungal cellulaseproduced from Humicola insolens and Humicola strain DSM1800 or acellulase 212-producing fungus belonging to the genus Aeromonas, andcellulase extracted from the hepatopancreas of a marine mollusk(Dolabella Auricula Solander), suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) isespecially useful.

Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. See also lipasesin Japanese Patent Application 53,20487, laid open to public inspectionon Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co.Ltd., Nagoya, Japan, under the trade name Lipase P "Amano," hereinafterreferred to as "Amano-P." Other commercial lipases include Amano-CES,lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.lipolyticum NRRLB 3673, commercially available from Toyo Jozo Co.,Tagata, Japan; and further Chromobacter viscosum lipases from U.S.Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipasesex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicolalanuginosa and commercially available from Novo (see also EPO 341,947)is a preferred lipase for use herein.

Peroxidase enzymes are used in combination with oxygen sources, e.g.,percarbonate, perborate, persulfate, hydrogen peroxide, etc. They areused for "solution bleaching," i.e. to prevent transfer of dyes orpigments removed from substrates during wash operations to othersubstrates in the wash solution. Peroxidase enzymes are known in theart, and include, for example, horseradish peroxidase, ligninase, andhaloperoxidase such as chloro- and bromo-peroxidase.Peroxidase-containing detergent compositions are disclosed, for example,in PCT International Application WO 89/099813, published Oct. 19, 1989,by O. Kirk, assigned to Novo Industries A/S.

A wide range of enzyme materials and means for their incorporation intosynthetic detergent compositions are also disclosed in U.S. Pat. No.3,553,139, issued Jan. 5, 1971 to McCarty et al. Enzymes are furtherdisclosed in U.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978,and in U.S. Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985, both.Enzyme materials useful for liquid detergent formulations, and theirincorporation into such formulations, are disclosed in U.S. Pat. No.4,261,868, Hora et al, issued Apr. 14, 1981. Enzymes for use indetergents can be stabilized by various techniques. Enzyme stabilizationtechniques are disclosed and exemplified in U.S. Pat. No. 3,600,319,issued Aug. 17, 1971 to Gedge, et al, and European Patent ApplicationPublication No. 0 199 405, Application No. 86200586.5, published Oct.29, 1986, Venegas. Enzyme stabilization systems are also described, forexample, in U.S. Pat. No. 3,519,570.

Enzyme Stabilizers

The enzymes employed herein are stabilized by the presence ofwater-soluble sources of calcium and/or magnesium ions in the finishedcompositions which provide such ions to the enzymes. (Calcium ions aregenerally somewhat more effective than magnesium ions and are preferredherein if only one type of cation is being used.) Additional stabilitycan be provided by the presence of various other art-disclosedstabilizers, especially borate species: see Severson, U.S. Pat. No.4,537,706. Typical detergents, especially liquids, will comprise fromabout 1 to about 30, preferably from about 2 to about 20, morepreferably from about 5 to about 15, and most preferably from about 8 toabout 12, millimoles of calcium ion per liter of finished composition.This can vary somewhat, depending on the amount of enzyme present andits response to the calcium or magnesium ions. The level of calcium ormagnesium ions should be selected so that there is always some minimumlevel available for the enzyme, after allowing for complexation withbuilders, fatty acids, etc., in the composition. Any water-solublecalcium or magnesium salt can be used as the source of calcium ormagnesium ions, including, but not limited to, calcium chloride, calciumsulfate, calcium malate, calcium maleate, calcium hydroxide, calciumformate, and calcium acetate, and the corresponding magnesium salts. Asmall amount of calcium ion, generally from about 0.05 to about 0.4millimoles per liter, is often also present in the composition due tocalcium in the enzyme slurry and formula water. In solid detergentcompositions the formulation may include a sufficient quantity of awater-soluble calcium ion source to provide such amounts in the laundryliquor. In the alternative, natural water hardness may suffice.

It is to be understood that the foregoing levels of calcium and/ormagnesium ions are sufficient to provide enzyme stability. More calciumand/or magnesium ions can be added to the compositions to provide anadditional measure of grease removal performance. Accordingly, as ageneral proposition the compositions herein will typically comprise fromabout 0.05% to about 2% by weight of a water-soluble source of calciumor magnesium ions, or both. The amount can vary, of course, with theamount and type of enzyme employed in the composition.

The compositions herein may also optionally, but preferably, containvarious additional stabilizers, especially borate-type stabilizers.Typically, such stabilizers will be used at levels in the compositionsfrom about 0.25% to about 10%, preferably from about 0.5% to about 5%,more preferably from about 0.75% to about 3%, by weight of boric acid orother borate compound capable of forming boric acid in the composition(calculated on the basis of boric acid). Boric acid is preferred,although other compounds such as boric oxide, borax and other alkalimetal borates (e.g., sodium ortho-, meta- and pyroborate, and sodiumpentaborate) are suitable. Substituted boric acids (e.g., phenylboronicacid, butane boronic acid, and p-bromo phenylboronic acid) can also beused in place of boric acid.

Bleaching Compounds--Bleaching Agents and Bleach Activators

The detergent compositions herein may optionally contain bleachingagents or bleaching compositions containing a bleaching agent and one ormore bleach activators. When present, bleaching agents will typically beat levels of from about 1% to about 30%, more typically from about 5% toabout 20%, of the detergent composition, especially for fabriclaundering. If present, the amount of bleach activators will typicallybe from about 0.1% to about 60%, more typically from about 0.5% to about40% of the bleaching composition comprising the bleachingagent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agentsuseful for detergent compositions in textile cleaning, hard surfacecleaning, or other cleaning purposes that are now known or become known.These include oxygen bleaches as well as other bleaching agents.Perborate bleaches, e.g., sodium perborate (e.g., mono- ortetra-hydrate) can be used herein.

Another category of bleaching agent that can be used without restrictionencompasses percarboxylic acid bleaching agents and salts thereof.Suitable examples of this class of agents include magnesiummonoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid anddiperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S.Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S. patentapplication Ser. No. 740,446, Burns et al, filed Jun. 3, 1985, EuropeanPatent Application 0,133,354, Banks et al, published Feb. 20, 1985, andU.S. Pat. No. 4,412,934, Chung et al, issued Nov. 1, 1983. Highlypreferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproicacid as described in U.S. Pat. No. 4,634,551, issued Jan. 6, 1987 toBurns et al.

Peroxygen bleaching agents can also be used. Suitable peroxygenbleaching compounds include sodium carbonate peroxyhydrate andequivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate,urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE,manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having anaverage particle size in the range from about 500 micrometers to about1,000 micrometers, not more than about 10% by weight of said particlesbeing smaller than about 200 micrometers and not more than about 10% byweight of said particles being larger than about 1,250 micrometers.Optionally, the percarbonate can be coated with silicate, borate orwater-soluble surfactants. Percarbonate is available from variouscommercial sources such as FMC, Solvay and Tokai Denka.

Mixtures of bleaching agents can also be used.

Peroxygen bleaching agents, the perborates, the percarbonates, etc., arepreferably combined with bleach activators. which lead to the in situproduction in aqueous solution (i.e., during the washing process) of theperoxy acid corresponding to the bleach activator. Various nonlimitingexamples of activators are disclosed in U.S. Pat. No. 4,915,854, issuedApr. 10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. Thenonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine(TAED) activators are typical, and mixtures thereof can also be used.See also U.S. Pat. No. 4,634,551 for other typical bleaches andactivators useful herein.

Highly preferred amido-derived bleach activators are those of theformulae:

    R.sup.1 N(R.sup.5)C(O)R.sup.2 C(O)L or R.sup.1 C(O)N(R.sup.5)R.sup.2 C(O)L

wherein R¹ is an alkyl group containing from about 6 to about 12 carbonatoms, R² is an alkylene containing from 1 to about 6 carbon atoms, R⁵is H or alkyl, aryl, or alkaryl containing from about 1 to about 10carbon atoms, and L is any suitable leaving group. A leaving group isany group that is displaced from the bleach activator as a consequenceof the nucleophilic attack on the bleach activator by the perhydrolysisanion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include(6-octanamidocaproyl)oxybenzenesulfonate,(6-nonanamidocaproyl)oxybenzenesulfonate,(6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof asdescribed in U.S. Pat. No. 4,634,551, incorporated herein by reference.

Another class of bleach activators comprises the benzoxazin-typeactivators disclosed by Hodge et al in U.S. Pat. No. 4,966,723, issuedOct. 30, 1990, incorporated herein by reference. A highly preferredactivator of the benzoxazin-type is: ##STR2##

Still another class of preferred bleach activators includes the acyllactam activators, especially acyl caprolactams and acyl valerolactamsof the formulae: ##STR3## wherein R⁶ is H or an alkyl, aryl, alkoxyaryl,or alkaryl group containing from 1 to about 12 carbon atoms. Highlypreferred lactam activators include benzoyl caprolactam, octanoylcaprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam,decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam,octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam,nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixturesthereof. See also U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8,1985, incorporated herein by reference, which discloses acylcaprolactams, including benzoyl caprolactam, adsorbed into sodiumperborate.

Bleaching agents other than oxygen bleaching agents are also known inthe art and can be utilized herein. One type of non-oxygen bleachingagent of particular interest includes photoactivated bleaching agentssuch as the sulfonated zinc and/or aluminum phthalocyanines. See U.S.Pat. No. 4,033,718, issued Jul. 5, 1977 to Holcombe et al. If used,detergent compositions will typically contain from about 0.025% to about1.25%, by weight, of such bleaches, especially sulfonate zincphthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of amanganese compound. Such compounds are well known in the art andinclude, for example, the manganese-based catalysts disclosed in U.S.Pat. Nos. 5,246,621, 5,244,594; 5,194,416; 5,114,606; and European Pat.App. Pub. Nos. 549,271A1, 549,272A1, 544,440A2, and 544,490A1; Preferredexamples of these catalysts include Mn^(IV) ₂ (u-O)₃(1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (PF₆)₂, Mn^(III) ₂ (u-O)₁(u-OAc)₂ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂₋ (ClO₄)₂, Mn^(IV) ₄(u-O)₆ (1,4,7-triazacyclononane)₄ (ClO₄)₄, Mn^(III) Mn^(IV) ₄ (u-O)₁(u-OAc)₂₋ (1,4,7-trimethyl-1,4,7-triazacyclononane)₂ (ClO₄)₃, Mn^(IV)(1,4,7-trimethyl-1,4,7-triazacyclononane)-(OCH₃)₃ (PF₆), and mixturesthereof. Other metal-based bleach catalysts include those disclosed inU.S. Pat. Nos. 4,430,243 and 5,114,611. The use of manganese withvarious complex ligands to enhance bleaching is also reported in thefollowing U.S. Pat. Nos. 4,728,455; 5,284,944; 5,246,612; 5,256,779;5,280,117; 5,274,147; 5,153,161; and 5,227,084.

As a practical matter, and not by way of limitation, the compositionsand processes herein can be adjusted to provide on the order of at leastone part per ten million of the active bleach catalyst species in theaqueous washing liquor, and will preferably provide from about 0.1 ppmto about 700 ppm, more preferably from about 1 ppm to about 500 ppm, ofthe catalyst species in the laundry liquor.

Polymeric Soil Release Agent

Any polymeric soil release agent known to those skilled in the art canoptionally be employed in the compositions and processes of thisinvention. Polymeric soil release agents are characterized by havingboth hydrophilic segments, to hydrophilize the surface of hydrophobicfibers, such as polyester and nylon, and hydrophobic segments, todeposit upon hydrophobic fibers and remain adhered thereto throughcompletion of washing and rinsing cycles and, thus, serve as an anchorfor the hydrophilic segments. This can enable stains occurringsubsequent to treatment with the soil release agent to be more easilycleaned in later washing procedures.

The polymeric soil release agents useful herein especially include thosesoil release agents having: (a) one or more nonionic hydrophilecomponents consisting essentially of (i) polyoxyethylene segments with adegree of polymerization of at least 2, or (ii) oxypropylene orpolyoxypropylene segments with a degree of polymerization of from 2 to10, wherein said hydrophile segment does not encompass any oxypropyleneunit unless it is bonded to adjacent moieties at each end by etherlinkages, or (iii) a mixture of oxyalkylene units comprising oxyethyleneand from 1 to about 30 oxypropylene units wherein said mixture containsa sufficient amount of oxyethylene units such that the hydrophilecomponent has hydrophilicity great enough to increase the hydrophilicityof conventional polyester synthetic fiber surfaces upon deposit of thesoil release agent on such surface, said hydrophile segments preferablycomprising at least about 25% oxyethylene units and more preferably,especially for such components having about 20 to 30 oxypropylene units,at least about 50% oxyethylene units; or (b) one or more hydrophobecomponents comprising (i) C₃ oxyalkylene terephthalate segments,wherein, if said hydrophobe components also comprise oxyethyleneterephthalate, the ratio of oxyethylene terephthalate:C₃ oxyalkyleneterephthalate units is about 2:1 or lower, (ii) C₄ -C₆ alkylene or oxyC₄ -C₆ alkylene segments, or mixtures therein, (iii) poly(vinyl ester)segments, preferably polyvinyl acetate), having a degree ofpolymerization of at least 2, or (iv) C₁ -C₄ alkyl ether or C₄hydroxyalkyl ether substituents, or mixtures therein, wherein saidsubstituents are present in the form of C₁ -C₄ alkyl ether or C₄hydroxyalkyl ether cellulose derivatives, or mixtures therein, and suchcellulose derivatives are amphiphilic, whereby they have a sufficientlevel of C₁ -C₄ alkyl ether and/or C₄ hydroxyalkyl ether units todeposit upon conventional polyester synthetic fiber surfaces and retaina sufficient level of hydroxyls, once adhered to such conventionalsynthetic fiber surface, to increase fiber surface hydrophilicity, or acombination of (a) and (b).

Typically, the polyoxyethylene segments of (a)(i) will have a degree ofpolymerization of from about 200, although higher levels can be used,preferably from 3 to about 150, more preferably from 6 to about 100.Suitable oxy C₄ -C₆ alkylene hydrophobe segments include, but are notlimited to, end-caps of polymeric soil release agents such as MO₃S(CH₂)_(n) OCH₂ CH₂ O--, where M is sodium and n is an integer from 4-6,as disclosed in U.S. Pat. No. 4,721,580, issued Jan. 26, 1988 toGosselink.

Polymeric soil release agents useful in the present invention alsoinclude cellulosic derivatives such as hydroxyether cellulosic polymers,copolymeric blocks of ethylene terephthalate or propylene terephthalatewith polyethylene oxide or polypropylene oxide terephthalate, and thelike. Such agents are commercially available and include hydroxyethersof cellulose such as METHOCEL (Dow). Cellulosic soil release agents foruse herein also include those selected from the group consisting of C₁-C₄ alkyl and C₄ hydroxyalkyl cellulose; see U.S. Pat. No. 4,000,093,issued Dec. 28, 1976 to Nicol, et al.

Soil release agents characterized by poly(vinyl ester) hydrophobesegments include graft copolymers of poly(vinyl ester), e.g., C₁ -C₆vinyl esters, preferably poly(vinyl acetate) grafted onto polyalkyleneoxide backbones, such as polyethylene oxide backbones. See EuropeanPatent Application 0 219 048, published Apr. 22, 1987 by Kud, et al.Commercially available soil release agents of this kind include theSOKALAN type of material, e.g., SOKALAN HP-22, available from BASF (WestGermany).

One type of preferred soil release agent is a copolymer having randomblocks of ethylene terephthalate and polyethylene oxide (PEO)terephthalate. The molecular weight of this polymeric soil release agentis in the range of from about 25,000 to about 55,000. See U.S. Pat. No.3,959,230 to Hays, issued May 25, 1976 and U.S. Pat. No. 3,893,929 toBasadur issued Jul. 8, 1975.

Another preferred polymeric soil release agent is a polyester withrepeat units of ethylene terephthalate units contains 10-15% by weightof ethylene terephthalate units together with 90-80% by weight ofpolyoxyethylene terephthalate units, derived from a polyoxyethyleneglycol of average molecular weight 300-5,000. Examples of this polymerinclude the commercially available material ZELCON 5126 (from Dupont)and MILEASE T (from ICI). See also U.S. Pat. No. 4,702,857, issued Oct.27, 1987 to Gosselink.

Another preferred polymeric soil release agent is a sulfonated productof a substantially linear ester oligomer comprised of an oligomericester backbone of terephthaloyl and oxyalkyleneoxy repeat units andterminal moieties covalently attached to the backbone. These soilrelease agents are described fully in U.S. Pat. No. 4,968,451, issuedNov. 6, 1990 to J. J. Scheibel and E. P. Gosselink. Other suitablepolymeric soil release agents include the terephthalate polyesters ofU.S. Pat. No. 4,711,730, issued Dec. 8, 1987 to Gosselink et al, theanionic end-capped oligomeric esters of U.S. Pat. No. 4,721,580, issuedJan. 26, 1988 to Gosselink, and the block polyester oligomeric compoundsof U.S. Pat. No. 4,702,857, issued Oct. 27, 1987 to Gosselink.

Preferred polymeric soil release agents also include the soil releaseagents of U.S. Pat. No. 4,877,896, issued Oct. 31, 1989 to Maldonado etal, which discloses anionic, especially sulfoarolyl, end-cappedterephthalate esters.

If utilized, soil release agents will generally comprise from about0.01% to about 10.0%, by weight, of the detergent compositions herein,typically from about 0.1% to about 5%, preferably, from about 0.2% toabout 3.0%.

Still another preferred soil release agent is an oligomer with repeatunits of terephthaloyl units, sulfoisoterephthaloyl units,oxyethyleneoxy and oxy-1,2-propylene units. The repeat units form thebackbone of the oligomer and are preferably terminated with modifiedisethionate end-caps. A particularly preferred soil release agent ofthis type comprises about one sulfoisophthaloyl unit, 5 terephthaloylunits, oxyethyleneoxy and oxy-1,2-propyleneoxy units in a ratio of fromabout 1.7 to about 1.8, and two end-cap units of sodium2-(2-hydroxyethoxy)-ethanesulfonate. Said soil release agent alsocomprises from about 0.5% to about 20%, by weight of the oligomer, of acrystalline-reducing stabilizer, preferably selected from the groupconsisting of xylene sulfonate, cumene sulfonate, toluene sulfonate, andmixtures thereof.

Process

Included in the present invention is a process for making a structureddetergent composition consisting essentially of the surfactant and thehydrophilic, finely-divided silica. The process comprises the step ofmixing an paste of the surfactant with the finely divided hydrophilicsilica, under adequate mixing to intimately combine the components intoan homogeneous mixture. The silica is well-dispersed in the structureddetergent composition. The resultant detergent composition has ahardened or firmer physical structure than the detergent surfactant.

Also included in the present invention is a process for making astructured surfactant composition for a detergent composition comprisingthe steps of:

a) Mixing from about 1% to about 20% of a hydrophilic, finely-dividedparticulate silica and from about 35% to about 60% of a detergentsurfactant, thereby forming a hardened paste;

b) Applying shear force to the hardened paste to form a flowable liquid;and

c) Dispersing the flowable liquid into fine droplets and agglomertingwith dry detergent powder comprising other detergent adjuvants selectedfrom the group consisting of other detergent surfactant, detergentbuilders, silica, and mixtures thereof, to form particles using a highspeed mixer.

The silica particulate is preferably a hydrophilic precipitated silicaand the detergent surfactant paste is an anionic surfactant, mostpreferably alkylalkoxy sulfate comprising an alkyl portion of from 6 to18 carbon atoms and an alkoxy portion comprising, an average, from about0.5 to about 20 moles of alkoxy, preferably ethoxy, units, morepreferably from about 0.5 to about 5 ethoxy units.

In order to make the structured surfactant composition, any suitableapparatus capable of handling viscous paste is required. Suitableapparatus includes, for example, twin-screw extruders, Teledynecompounders, etc.

In order to make a detergent composition comprising the structuredsurfactant composition, suitable apparatus includes, for example,mixers/agglomerators can be used. In one preferred embodiment, theprocess of the invention is continuously carried out.

The process preferably further comprises another step wherein thegranulated surfactant composition is dusted with silica or zeolite.

EXAMPLES Example 1

The structured surfactant composition can be made in the following way:the hydrophilic silica particulate is mixed with an alkylethoxy sulfatepaste in a single-screw or twin-screw extruder. The pre-mix of soda ash,builder, zeolite and precipitated silica is agglomerated with thestructured surfactant composition in a plowshare mixer. The resultingparticle has a density of 600 to 800 g/l.

Example 2

    ______________________________________                                        Ingredient            %                                                       ______________________________________                                        CFAS                  21                                                      CFA                   1                                                       AE45-T                0.8                                                     Structured Surfactant Composition*                                                                  3.3                                                     of Example 1                                                                  STPP                  22.5                                                    Zeolite               12.6                                                    Polymer               0.7                                                     Other detergent adjuvants                                                                           Balance                                                 ______________________________________                                         *Structured surfactant composition is comprised of AE3S at 70%,               Hydrophilic precipitated silica at 2% and water at 28%.                  

Example 3

    ______________________________________                                        Ingredient            %                                                       ______________________________________                                        LAS                   20.7                                                    STPP                  22.7                                                    Carbonate             22                                                      Zeolite               14                                                      Structured surfactant Composition*                                                                  3.3                                                     of Example 1                                                                  Other detergent adjuvants                                                                           Balance                                                 ______________________________________                                         *Structured surfactant composition is comprised of AE3S at 70%,               Hydrophilic precipitated silica at 2% and water at 28%.                  

Example 4

    ______________________________________                                        Ingredient           %                                                        ______________________________________                                        LAS                  24.5                                                     STPP                 17.9                                                     Soda Ash             30                                                       Zeolite              11.9                                                     Surfactant Composition (AE3S)*                                                                     3.3                                                      of Example 1                                                                  Other detergent adjuvants                                                                          Balance                                                  ______________________________________                                         *Structured surfactant composition is comprised of AE3S at 70%,               Hydrophilic precipitated silica at 2% and water at 28%.                  

What is claimed is:
 1. A structured surfactant composition consistingessentially of:(a) from about 35% to about 60% of a detergentsurfactant; (b) from about 1% to about 20% of a hydrophilic,finely-divided silica particulate having an average surface area of fromabout to about 140 m² /g to 550 m² /g; and (c) from about 15% to about25% moisture.
 2. A surfactant composition according to claim 1, whereinthe detergent surfactant is selected from the group consisting ofanionic, cationic, zwitterionic, ampholytic surfactants and mixturesthereof.
 3. A surfactant composition according to claim 2, wherein thesilica particulate is hydrophilic precipitated silica.
 4. A surfactantcomposition according to claim 3, wherein the detergent surfactant isalkyl ether sulfate of the formula R--E_(n) SO₃ M, wherein:(i) R isC8-20 alkyl chain; (ii) E is an ethoxy unit; (iii) n is from 1-20; and(iv) M is a cation.
 5. A granular detergent composition comprising:(a)from about 2% to about 70% of a structured surfactant composition, thesurfactant composition consisting essentially of:(i) from about 35% toabout 60% of a detergent surfactant; (ii) from about 1% to about 20% ofa hydrophilic, finely-divided silica particulate having an averagesurface area of from about to about 140 m² /g to 550 m² /g; and (iii)from about 15% to about 25% moisture; and (b) from about 30% to about98% of other detergent adjuvants selected from the group consisting ofother detergent surfactants, detergent builders, silica, and mixturesthereof.
 6. A composition according to claim 5, wherein the detergentsurfactant in (a)(i) is anionic surfactant and the silica particulate in(a)(ii) is hydrophilic precipitated silica.
 7. A composition accordingto claim 6, wherein the anionic surfactant is an alkyl ether sulfate ofthe formula R--E_(n) --SO₃ M, wherein:(a) R is C12-18, alkyl chain; (b)E is an ethoxy unit; (c) n is from 1-20; and (d) M is a cation.
 8. Aprocess for making a surfactant composition for a detergent compositioncomprising the steps of:a) mixing from about 1% to about 20% of ahydrophilic, finely-divided particulate silica having an average surfacearea of from about to about 140 m² /g to 550 m² /g, from about 35% toabout 60% of a detergent surfactant, and from about 15% to about 25%moisture, thereby forming a hardened paste; b) applying shear force tothe hardened paste to form a flowable liquid; and c) dispensing theflowable liquid into fine droplets and agglomerating with dry detergentpowder comprising other detergent adjuvants selected from the groupconsisting of other detergent surfactants, detergent builders, silica,and mixtures thereof, to form particles using a high speed mixer.
 9. Aprocess according to claim 8, wherein the silica particulate is ahydrophilic precipitated silica and the detergent surfactant is ananionic surfactant paste.
 10. A process for making a surfactantcomposition for a detergent composition comprising the steps of:a)mixing from about 1% to about 20% of a hydrophilic, finely-dividedparticulate silica having an average surface area of from about to about140 m² /g to 550 m² /g, from about 15% to about 25% moisture, and fromabout 35% to about 60% of an alkyl ethyl surfactant of the formulaR--E_(n) --SO₃ M, whereinR is C₁₂₋₁₅, alkyl chain; E is an ethoxy unit;n is 3; and M is a sodium ion, thereby forming a structured surfactantcomposition; and b) granulating the surfactant composition upon mixingwith a dry detergent powder comprising other detergent adjuvantsselected from the group consisting of other detergent surfactantsdetergent builders, silica, and mixtures thereof.